CN109314279B - Lithium secondary battery electrolyte and lithium secondary battery comprising same - Google Patents

Lithium secondary battery electrolyte and lithium secondary battery comprising same Download PDF

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CN109314279B
CN109314279B CN201780037464.1A CN201780037464A CN109314279B CN 109314279 B CN109314279 B CN 109314279B CN 201780037464 A CN201780037464 A CN 201780037464A CN 109314279 B CN109314279 B CN 109314279B
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lithium secondary
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CN109314279A (en
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朴寭真
赵仁行
金相勋
申又澈
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present disclosure relates to a lithium secondary battery electrolyte and a lithium secondary battery including the same, the lithium secondary battery electrolyte including: a non-aqueous organic solvent including a branched ester solvent represented by formula 1; and a lithium salt.

Description

Lithium secondary battery electrolyte and lithium secondary battery comprising same
Technical Field
The present disclosure relates to an electrolyte for a lithium secondary battery and a lithium secondary battery including the same.
Background
A lithium secondary battery, which has recently received attention as a power source for small portable electronic devices, uses an organic electrolytic solution, and thus has a discharge voltage twice as high as that of a conventional battery using an alkaline aqueous solution, and thus has a high energy density.
As for the anode active material of the lithium secondary battery, various carbon-based materials, such as artificial graphite, natural graphite, and hard carbon, which can intercalate and deintercalate lithium, have been used.
As for the positive electrode active material, a chalcogenide compound is mainly used, and an example thereof may be a composite metal oxide such as LiCoO2、LiMn2O4、LiNiO2、LiNi1-xCoxO2(0<x<1)、LiMnO2And the like.
As the electrolytic solution, a lithium salt dissolved in a nonaqueous solvent (such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, or the like) is used.
During initial charging of the lithium secondary battery, lithium ions released from the lithium transition metal oxide, i.e., the positive electrode, are transferred into the carbon negative electrode and are intercalated therein. Because of its high reactivity, lithium reacts with the carbon negative electrode to produce Li2CO3LiO, LiOH, etc., thereby forming a thin film on the surface of the negative electrode. This film is called a Solid Electrolyte Interface (SEI) film. The SEI film formed during initial charging prevents a reaction between lithium ions and a carbon negative electrode or other materials during charging and discharging. In addition, it also acts as an ion tunnel, allowing the passage of lithium ions. The ion tunneling prevents the collapse of the structure of the carbon negative electrode due to the co-intercalation of the organic solvent having a high molecular weight and the solvated lithium ions into the carbon negative electrode. Once the SEI film is formed, lithium ions no longer react with the carbon electrode or other materials, so that the amount of lithium ions is reversibly maintained.
However, gas is generated inside the battery using the carbonate-based organic solvent due to decomposition of the carbonate-based organic solvent during the reaction for forming the SEI film. These gases include H depending on the type of non-aqueous organic solvent and anode active material used2、CO、CO2、CH4、C2H6、C3H8、C3H6And the like. Due to gas generated inside the battery, the battery swells in the thickness direction when the battery is charged, and when the battery is fully charged and maintained at a high temperature, the SEI film is gradually decomposed by electrochemical energy and thermal energy, which increase with the passage of time, continuously causing a new adjacent surface of the negative electrode and exposed electrolyte solutionThe reaction of (1). The continuous generation of gas increases the internal pressure inside the battery.
There is a need to develop a new electrolyte composition capable of changing the reaction of forming the SEI film and suppressing the increase of internal pressure when exposed to high temperature, and simultaneously improving capacity retention.
Disclosure of Invention
Technical problem
Embodiments of the present invention provide an electrolyte for a lithium secondary battery having improved high-voltage, high-temperature characteristics.
Another embodiment of the present invention provides a lithium secondary battery including the electrolyte for a lithium secondary battery.
Technical scheme
Embodiments of the present invention provide an electrolyte for a lithium secondary battery including a non-aqueous organic solvent including a branched ester-based solvent represented by chemical formula 1 and a lithium salt.
[ chemical formula 1]
Figure BDA0001906733310000021
In the chemical formula 1, the first and second,
R1to R4The same or different and independently are C1 to C5 straight or branched chain alkyl groups.
The branched ester solvent represented by chemical formula 1 may be selected from the group consisting of: a compound represented by chemical formula 2-1 to a compound represented by chemical formula 2-8, and combinations thereof.
Figure BDA0001906733310000022
Figure BDA0001906733310000031
The non-aqueous organic solvent may further include a solvent selected from the group consisting of: a carbonate-based solvent, a linear ester-based solvent represented by chemical formula 3, and a combination thereof.
[ chemical formula 3]
Figure BDA0001906733310000032
In the chemical formula 3, the first and second,
R5and R6The same or different and independently are C1 to C5 straight chain alkyl groups.
The carbonate-based solvent may be selected from the group consisting of: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Methyl Ethyl Carbonate (MEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), and combinations thereof.
The linear ester solvent represented by chemical formula 3 may be selected from the group consisting of: methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, and combinations thereof.
The non-aqueous organic solvent may include about 10 wt% to about 40 wt% of the branched ester-based solvent represented by chemical formula 1, based on the total amount of the non-aqueous organic solvent.
The non-aqueous organic solvent may include a branched ester-based solvent represented by chemical formula 1, a carbonate-based solvent, and a linear ester-based solvent represented by chemical formula 3, wherein the non-aqueous organic solvent includes about 100 to about 400 parts by weight of the carbonate-based solvent and about 50 to about 150 parts by weight of the linear ester-based solvent represented by chemical formula 3, based on 100 parts by weight of the branched ester-based solvent represented by chemical formula 1.
The electrolyte for a lithium secondary battery may further include an electrolyte additive for a lithium secondary battery.
The electrolyte additive for a lithium secondary battery is selected from the group consisting of: ethylene carbonate-based compounds represented by chemical formula 5, alkanesultone, vinylene carbonate, and combinations thereof.
[ chemical formula 5]
Figure BDA0001906733310000033
In the chemical formula 5, the first and second organic solvents,
R7and R8The same or different and independently selected from the group consisting of: hydrogen, halogen, Cyano (CN), Nitro (NO)2) Vinyl and fluorinated C1 to C5 straight or branched chain alkyl, provided that R7And R8Not all are hydrogen.
The alkanesultone may be selected from the group consisting of: 1, 3-propane sultone, butane sultone, 1,3- (1-propene sultone), and combinations thereof.
The electrolyte for a lithium secondary battery may include about 6 wt% to about 13 wt% of an electrolyte additive for a lithium secondary battery, based on the total weight of the electrolyte for a lithium secondary battery.
The electrolyte for the lithium secondary battery may include fluoroethylene carbonate (FEC), 1, 3-propane sultone (1,3-PS), and ethylene carbonate (VEC) as electrolyte additives for the lithium secondary battery.
Here, the electrolyte additive for a lithium secondary battery may include about 1,000 parts by weight to about 2,000 parts by weight of fluoroethylene carbonate (FEC) and about 100 parts by weight to about 500 parts by weight of 1, 3-propane sultone, based on 100 parts by weight of ethylene vinyl carbonate (VEC).
Another embodiment of the present invention provides a lithium secondary battery including: a positive electrode including a positive active material; a negative electrode including a negative active material; and an electrolyte for a lithium secondary battery.
The positive electrode active material may be selected from compounds represented by the following chemical formula. LiaA1-bDbE2(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0 and less than or equal to 0.5 in the chemical formula); liaG1-bDbO2-cEc(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05); LiG2-bDbO4-cEc(wherein, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05) in the chemical formula; liaNi1-b-cCobDcEα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2)；LiaNi1-b-cCobDcO2-αJα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNi1-b-cCobDcO2-αJ2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNi1-b-cMnbDcEα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2)；LiaNi1-b-cMnbDcO2-αJα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNi1-b-cMnbDcO2-αJ2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNibGcLdO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0.001 and less than or equal to 0.2); liaNibGcO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, and c is more than or equal to 0 and less than or equal to 0.5); liaNibCocMndLeO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0.001 and less than or equal to 0.2); liaNibCocMndO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0 and less than or equal to 0.5); liaNiLbO2(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula); liaCoLbO2(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula); liaMnLbO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001≤0.2)；LiaMn2LbO4(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula); liaMn2O4(wherein, a is more than or equal to 0.90 and less than or equal to 1.8 in the chemical formula); MO (metal oxide semiconductor)2；MS2；LiMS2；V2O5；LiV2O5；LiQO2；LiNiVO4；Li(3-f)T2(PO4)3(wherein, f is more than or equal to 0 and less than or equal to 2 in the chemical formula); li(3-f)Fe2(PO4)3(wherein, f is more than or equal to 0 and less than or equal to 2 in the chemical formula); LiFePO4
Wherein formula A is selected from the group consisting of: ni, Co, Mn and combinations thereof, D is selected from the group consisting of: al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and combinations thereof, E is selected from the group consisting of: o, F, S, P and combinations thereof, G is selected from the group consisting of: co, Mn, and combinations thereof, J is selected from the group consisting of: F. s, P, and combinations thereof, L is a transition metal or lanthanide selected from the group consisting of: mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, P, As, Sb, Bi, S, Se, Te, Po, Mn, La, Ce and combinations thereof, M being selected from the group consisting of: ti, Mo, Mn and combinations thereof, Q is selected from the group consisting of: cr, V, Fe, Sc, Ti, Y, and combinations thereof, and T is selected from the group consisting of: v, Cr, Mn, Co, Ni, Cu, and combinations thereof.
Specifically, the positive active material may be LiCoO2。
The negative active material may be graphite.
The lithium secondary battery may have a charging voltage of about 4.3V or more.
Specifically, the lithium secondary battery may have a charging voltage of about 4.4V to about 4.5V.
Other embodiments of the invention are included in the following detailed description.
Advantageous effects
The electrolyte for a lithium secondary battery according to an embodiment of the present invention may have improved high voltage, high temperature characteristics, and thus improve the high voltage, high temperature characteristics of a lithium secondary battery including the electrolyte for a lithium secondary battery.
Drawings
Fig. 1 is a schematic view showing a lithium secondary battery according to an embodiment.
Fig. 2 is a graph showing changes in discharge capacity of the lithium secondary batteries manufactured in example 1, comparative example 1, and comparative example 4.
Fig. 3 is a graph showing changes in holding capacity of the lithium secondary batteries manufactured in example 1, comparative example 1, and comparative example 4.
Fig. 4 is a graph showing changes in thickness of the lithium secondary batteries manufactured in example 1, comparative example 1, and comparative example 4.
Fig. 5 is a graph showing changes in internal resistance of the lithium secondary batteries manufactured in example 1, comparative example 1, and comparative example 4.
Detailed Description
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of the claims.
In the present specification, when a specific definition is not otherwise provided, "alkyl" refers to a C1 to C5 linear or branched alkyl group, specifically to a C1 to C3 linear or branched alkyl group, and more specifically to a C1 or C2 alkyl group.
In the present specification, when a definition is not otherwise provided, "combination" refers to a mixture or an alloy.
According to an embodiment of the present invention, an electrolyte for a lithium secondary battery includes a non-aqueous organic solvent including a branched ester solvent represented by chemical formula 1 and a lithium salt.
[ chemical formula 1]
Figure BDA0001906733310000061
In the chemical formula 1, the first and second,
R1to R4Identical or different and independently are C1 to C5 linear or branched alkyl groups, specifically C1 to C3 linear or branched alkyl groups, and more specifically C1 or C2 alkyl groups.
The non-aqueous organic solvent serves as a medium for transferring ions participating in the electrochemical reaction of the lithium secondary battery.
When the electrolyte for a lithium secondary battery includes a non-aqueous organic solvent including a branched ester solvent represented by chemical formula 1, the bulky side chain of the branched ester solvent represented by chemical formula 1 protects α -carbon from attack of a nucleophile and thus may prevent side reactions, and also suppresses decomposition of the non-aqueous organic solvent during charge/discharge at a high voltage and thus may reduce a thickness expansion rate and an Internal Resistance (IR) increase rate of the lithium secondary battery, and in addition, effectively improves capacity characteristics and cycle life characteristics of the lithium secondary battery.
Specifically, the branched ester solvent represented by chemical formula 1 may be selected from the group consisting of: the compound represented by chemical formula 2-1 to the compound represented by chemical formula 2-8, and combinations thereof, but the branched ester solvent represented by chemical formula 1 is not limited thereto.
Figure BDA0001906733310000062
Figure BDA0001906733310000071
The non-aqueous organic solvent may further include a solvent selected from the group consisting of: a carbonate-based solvent, a linear ester-based solvent represented by chemical formula 3, and a combination thereof.
[ chemical formula 3]
Figure BDA0001906733310000072
In the chemical formula 3, the first and second,
R5and R6The same or different and independently are C1 to C5 linear alkyl groups, specifically C1 to C3 linear alkyl groups, and more specifically C1 or C2 alkyl groups.
The carbonate-based solvent may be selected from the group consisting of: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Methyl Ethyl Carbonate (MEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), and combinations thereof.
The linear ester solvent represented by chemical formula 3 may be selected from the group consisting of: methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, Ethyl Propionate (EP), n-propyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, and combinations thereof.
In addition to the branched ester solvent represented by chemical formula 1, when the non-aqueous organic solvent further includes a solvent selected from the group consisting of: a carbonate-based solvent, a linear ester-based solvent represented by chemical formula 3, and a combination thereof.
The non-aqueous organic solvent may include the branched ester-based solvent represented by chemical formula 1 in an amount of about 10 wt% to about 40 wt%, specifically about 10 wt% to about 30 wt%, and more specifically about 15 wt% to about 20 wt%, based on the total amount of the non-aqueous organic solvent. When the non-aqueous organic solvent includes the branched ester solvent represented by chemical formula 1 within this range, the thickness expansion rate and the Internal Resistance (IR) increase rate of the lithium secondary battery can be effectively reduced by effectively preventing side reactions and effectively inhibiting decomposition of the non-aqueous organic solvent during charge/discharge at a high voltage, and in addition, the capacity characteristics and cycle life characteristics of the lithium secondary battery can be effectively improved.
When the non-aqueous organic solvent includes the branched ester-based solvent represented by chemical formula 1, the carbonate-based solvent, and the linear ester-based solvent represented by chemical formula 3, the non-aqueous organic solvent includes the carbonate-based solvent in an amount of about 100 parts by weight to about 400 parts by weight, specifically about 150 parts by weight to about 350 parts by weight, and more specifically about 200 parts by weight to about 300 parts by weight, and the linear ester-based solvent represented by chemical formula 3 in an amount of about 50 parts by weight to about 150 parts by weight, specifically about 75 parts by weight to about 150 parts by weight, and more specifically about 75 parts by weight to about 100 parts by weight, based on 100 parts by weight of the branched ester-based solvent represented by chemical formula 1. When the non-aqueous organic solvent has a composition within this range, the thickness expansion rate and the Internal Resistance (IR) increase rate of the lithium secondary battery can be effectively reduced by effectively inhibiting the decomposition of the non-aqueous organic solvent during charge/discharge at a high voltage, and in addition, the capacity characteristics and cycle life characteristics of the lithium secondary battery can be effectively improved.
The non-aqueous organic solvent may further include a cyclic ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, an aprotic solvent, or an aromatic hydrocarbon solvent, as required, but is not limited thereto.
The cyclic ester solvent can be gamma-butyrolactone, decalactone, valerolactone, mevalonolactone, caprolactone, etc.
The ether solvent may be dimethyl ether, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, Tetrahydrofuran (THF), etc.
The ketone solvent can be cyclohexanone, etc.
The alcohol solvent can be ethanol, isopropanol, etc.
The aprotic solvent may be a nitrile represented by R — CN (wherein R may include a C2 to C20 linear, branched or cyclic hydrocarbon group, a double bond, an aromatic ring or an ether bond), or the like; amides such as Dimethylformamide (DMF), Dimethylacetamide (DMAC), and the like; dioxolanes such as 1, 3-dioxolane and the like; sulfolane; cycloalkanes such as cyclohexane, etc.
The aromatic hydrocarbon solvent may use an aromatic hydrocarbon compound represented by chemical formula 4.
[ chemical formula 4]
Figure BDA0001906733310000081
In the chemical formula 4, the first and second organic solvents,
R11to R16The same or different and independently selected from the group consisting of: hydrogen, halogenC1 to C10 alkyl, C1 to C10 haloalkyl, and combinations thereof.
Specific examples of the aromatic hydrocarbon solvent may be selected from the group consisting of: benzene, fluorobenzene, 1, 2-difluorobenzene, 1, 3-difluorobenzene, 1, 4-difluorobenzene, 1,2, 3-trifluorobenzene, 1,2, 4-trifluorobenzene, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, 1,2, 3-trichlorobenzene, 1,2, 4-trichlorobenzene, iodobenzene, 1, 2-diiodobenzene, 1, 3-diiodobenzene, 1, 4-diiodobenzene, 1,2, 3-triiodobenzene, 1,2, 4-triiodobenzene, toluene, fluorotoluene, 1, 2-difluorotoluene, 1, 3-difluorotoluene, 1, 4-difluorotoluene, 1,2, 3-trifluorotoluene, 1,2, 4-trifluorotoluene, chlorotoluene, 1, 2-dichlorotoluene, 1, 3-dichlorotoluene, 1, 4-difluorotoluene, 1, 3-difluorotoluene, 1, 4-difluorotoluene, 1,2, 3-trifluorotoluene, 1,2, 4-trifluorotoluene, chlorotoluene, 1, 2-dichlorotoluene, 1, 4-dichlorotoluene, 1,2, 3-trichlorotoluene, 1,2, 4-trichlorotoluene, iodotoluene, 1, 2-diiodotoluene, 1, 3-diiodotoluene, 1, 4-diiodotoluene, 1,2, 3-triiodotoluene, 1,2, 4-triiodotoluene, xylene, and combinations thereof.
The solvent further included in the non-aqueous organic solvent may be used alone or in a mixture, and when the organic solvent is used in a mixture, the mixture ratio may be controlled according to desired battery performance.
The lithium salt is dissolved in a non-aqueous organic solvent, serves as a source of lithium ions in the lithium secondary battery to operate the lithium secondary battery, and facilitates transport of the lithium ions between the positive electrode and the negative electrode. In addition, a lithium salt may serve as an auxiliary electrolytic salt.
The lithium salt may include one selected from the group consisting of: LiPF6、LiBF4、LiSbF6、LiAsF6、LiCF3SO3、LiN(SO2C2F5)2、LiN(SO2CF3)2、LiN(SO3C2F5)2、LiC4F9SO3、LiClO4、LiAlO4、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) (wherein x and y are natural numbers), LiCl, LiI, LiB (C)2O4)2[ lithium bis (oxalate) borate, LiBOB)]And combinations thereof, but is not limited thereto.
The concentration of the lithium salt may be about 0.1M to about 2.0M, and specifically about 0.5M to about 2.0M. When the concentration of the lithium salt is within this range, the electrolyte may have excellent performance and effective lithium ion mobility due to optimal electrolyte conductivity and viscosity.
The electrolyte for a lithium secondary battery may further include an electrolyte additive for a lithium secondary battery in order to improve the cycle life of the battery.
The electrolyte additive for the lithium secondary battery may be selected from the group consisting of: ethylene carbonate-based compounds represented by chemical formula 5, alkanesultone, vinylene carbonate, and combinations thereof.
[ chemical formula 5]
Figure BDA0001906733310000091
In the chemical formula 5, the first and second organic solvents,
R7and R8The same or different and independently selected from the group consisting of: hydrogen, halogen, Cyano (CN), Nitro (NO)2) Vinyl and fluorinated C1 to C5 straight or branched chain alkyl, provided that R7And R8Not all are hydrogen.
The ethylene carbonate-based compound represented by chemical formula 5 may be selected from the group consisting of: difluoroethylene carbonate, chlorinated ethylene carbonate, dichloroethylene carbonate, brominated ethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate (FEC), Vinyl Ethylene Carbonate (VEC), and combinations thereof, but is not limited thereto.
The alkanesultone may be selected from the group consisting of: 1, 3-propane sultone (1,3-PS), butane sultone, 1,3- (1-propene sultone), and combinations thereof, but is not limited thereto.
The electrolyte for a lithium secondary battery may include about 6 wt% to about 13 wt%, specifically about 6 wt% to about 10 wt%, and more specifically about 8 wt% to about 9.5 wt% of the electrolyte additive for a lithium secondary battery, based on the total weight of the electrolyte for a lithium secondary battery. When the amount of the electrolyte additive used for the lithium secondary battery is within this range, the cycle-life characteristics of the lithium secondary battery can be effectively improved.
Specifically, the electrolyte for the lithium secondary battery may include fluoroethylene carbonate (FEC), 1, 3-propane sultone (1,3-PS), and ethylene carbonate (VEC) as electrolyte additives for the lithium secondary battery. When the electrolyte for a lithium secondary battery includes the electrolyte additive for a lithium secondary battery having the above-described composition, cycle life characteristics may be improved and a thickness expansion rate of the lithium secondary battery may be reduced.
Here, the electrolyte additive for a lithium secondary battery may include fluoroethylene carbonate (FEC) in an amount of about 1,000 parts by weight to about 2,000 parts by weight, specifically about 1,000 parts by weight to about 1,400 parts by weight, and more specifically about 1,200 parts by weight to about 1,400 parts by weight and 1, 3-propane sultone in an amount of about 100 parts by weight to about 500 parts by weight, specifically about 200 parts by weight to about 500 parts by weight, and more specifically about 400 parts by weight to about 500 parts by weight, based on 100 parts by weight of ethylene vinyl carbonate (VEC). When the ratio of the amounts of the components of the electrolyte additive for a lithium secondary battery is within this range, the cycle life characteristics can be effectively improved.
Another embodiment of the present invention provides a lithium secondary battery including: a positive electrode including a positive active material; a negative electrode including a negative active material; and an electrolyte for a lithium secondary battery.
The positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material.
The positive electrode active material may include a compound (lithiated intercalation compound) that can reversibly intercalate and deintercalate lithium ions.
Specifically, the cathode active material may be one compound represented by the following chemical formula, but is not limited thereto.
LiaA1-bDbE2(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0 and less than or equal to 0.5 in the chemical formula); liaG1-bDbO2-cEc(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05); LiG2-bDbO4-cEc(wherein, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05) in the chemical formula; liaNi1-b-cCobDcEα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2)；LiaNi1-b-cCobDcO2-αJα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNi1-b-cCobDcO2-αJ2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNi1-b-cMnbDcEα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2)；LiaNi1-b-cMnbDcO2-αJα(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNi1-b-cMnbDcO2-αJ2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2)；LiaNibGcLdO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0.001 and less than or equal to 0.2); liaNibGcO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, and c is more than or equal to 0 and less than or equal to 0.5); liaNibCocMndLeO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0.001 and less than or equal to 0.2); liaNibCocMndO2(wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0 and less than or equal to 0.5); liaNiLbO2(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula); liaCoLbO2(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula); liaMnLbO2(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula); liaMn2LbO4(wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula); liaMn2O4(wherein, a is more than or equal to 0.90 and less than or equal to 1.8 in the chemical formula); MO (metal oxide semiconductor)2；MS2；LiMS2；V2O5；LiV2O5；LiQO2；LiNiVO4；Li(3-f)T2(PO4)3(wherein, f is more than or equal to 0 and less than or equal to 2 in the chemical formula); li(3-f)Fe2(PO4)3(wherein, f is more than or equal to 0 and less than or equal to 2 in the chemical formula); LiFePO4
Wherein formula A is selected from the group consisting of: ni, Co, Mn and combinations thereof, D is selected from the group consisting of: al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and combinations thereof, E is selected from the group consisting of: o, F, S, P and combinations thereof, G is selected from the group consisting of: co, Mn, and combinations thereof, J is selected from the group consisting of: F. s, P, and combinations thereof, L is a transition metal or lanthanide selected from the group consisting of: mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, P, As, Sb, Bi, S, Se, Te, Po, Mn, La, Ce and combinations thereof, M being selected from the group consisting of: ti, Mo, Mn and combinations thereof, Q is selected from the group consisting of: cr, V, Fe, Sc, Ti, Y, and combinations thereof, and T is selected from the group consisting of: v, Cr, Mn, Co, Ni, Cu, and combinations thereof.
A more specific example of the positive electrode active material may be LiCoO2. When LiCoO is included2When used as a positive electrode active material, the lithium secondary battery can effectively improve high-pressure and high-temperature characteristics.
The positive active material may include a positive active material having a coating layer, or a compound of an active material and an active material coated with a coating layer. The coating may comprise at least one coating element compound selected from the group consisting of: oxides and hydroxides of the coating elements, oxyhydroxides of the coating elements, oxycarbonates of the coating elements and hydroxycarbonates of the coating elements. The compounds used for the coating may be amorphous or crystalline. The coating elements included in the coating may be selected from the group consisting of: mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, and combinations thereof. The coating method may include any conventional method as long as it does not cause any side effect on the characteristics of the positive electrode active material (e.g., spraying, dipping), which is well known to those of ordinary skill in the art, and thus a detailed description thereof is omitted.
The positive active material layer further includes a binder and a conductive material.
The binder improves the binding characteristics of the positive electrode active material particles to each other and to the current collector, and examples of the binder include at least one of the following: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy, nylon, and the like, but is not limited thereto.
The conductive material improves the conductivity of the negative electrode, any conductive material may be used as the conductive agent unless it causes a chemical change, and examples of the conductive material include at least one selected from the group consisting of: natural graphite, artificial graphite, carbon black, Super-P (MMM corporation), acetylene black, ketjen black, hard carbon obtained by sintering at high temperature, soft carbon (carbon obtained by sintering at low temperature), carbon fiber, metal powder or metal fiber including copper, nickel, aluminum, silver, or the like; conductive polymers such as polyphenylene derivatives and the like; or mixtures thereof.
The cathode current collector may use aluminum (Al), but is not limited thereto.
The anode includes a current collector and an anode active material layer disposed thereon. The negative electrode active material layer includes a negative electrode active material.
The negative active material includes a material that reversibly intercalates/deintercalates lithium ions, lithium metal, a lithium metal alloy, a material capable of doping and dedoping lithium, or a transition metal oxide.
Materials that can reversibly intercalate/deintercalate lithium ions include carbon materials. The carbon material may be any carbon-based negative active material commonly used in lithium ion rechargeable batteries. Examples of the carbon material include crystalline carbon, amorphous carbon and a mixture thereof. The crystalline carbon may be amorphous, or natural graphite or artificial graphite in the form of flakes, spheres or fibers. The amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbonization products, coke, and the like.
Examples of lithium metal alloys include lithium and metals selected from the group consisting of: na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, Sn, Ti, Ag, Cd, Ga, Bi, and combinations thereof.
Materials capable of doping and dedoping lithium may include Si, SiOx(0<x<2) Si-Y alloy (wherein Y is an element selected from the group consisting of: alkali metals, alkaline earth metals, group 13 to group 16 elements, transition metals, rare earth elements and combinations thereof, and not Si), Sn, SnO2At least one of these materials may be mixed with SiO, Sn-C composite, Sn-Y (wherein Y is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 to group 16 elements, transition metals, rare earth elements, and combinations thereof and is not Sn)2Mixed and, in addition, carbon may be further deposited on the surface of the material capable of doping with lithium. Coating the surface of the above material with carbon can be performed by: organic materials such as ethylene, Tetrahydrofuran (THF) and cyclohexanone are decomposed in the presence of the above materials in vacuum at a high temperature of 800 ℃ or more, but not limited thereto. The element Y may be selected from the group consisting of: mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po and combinations thereof.
The transition metal oxide may include vanadium oxide, lithium vanadium oxide, and the like.
A more specific example of the negative active material may be graphite. When graphite is included as a negative active material, high-voltage, high-temperature characteristics of the lithium secondary battery can be effectively improved.
The negative active material layer may include a binder and optionally a conductive material.
The binder improves the binding property of the anode active material particles to each other and to the current collector, and specific examples may be polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acryl-acylated styrene-butadiene rubber, epoxy resin, nylon, and the like, but are not limited thereto.
The conductive material improves the conductivity of the negative electrode, and any conductive material may be used as the conductive agent unless it causes a chemical change, and examples thereof may include carbon-based materials such as natural graphite, artificial graphite, carbon black, Super-P (MMM corporation), acetylene black, ketjen black, hard carbon, soft carbon, carbon fiber, and the like; metal powders or metal fibers including copper, nickel, aluminum, silver, and the like; conductive polymers such as polyphenylene derivatives and the like; or mixtures thereof.
The current collector may be selected from the group consisting of: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, conductive metal coated polymer substrates, and combinations thereof.
The anode and the cathode may be manufactured by a method including: the active material, the conductive material, and the binder are mixed to an active material composition, and the composition is coated on the current collector. Electrode manufacturing methods are well known and therefore not described in detail in this specification. The solvent includes N-methylpyrrolidone, etc., but is not limited thereto.
The charging voltage of the lithium secondary battery may be about 4.3V or more, specifically about 4.4V to about 4.5V, and more specifically about 4.45V to about 4.5V, but is not limited thereto. A lithium secondary battery including the electrolyte for a lithium secondary battery according to an embodiment of the present invention may operate efficiently at a high charge voltage within this range.
The lithium secondary battery may further include a separator between the cathode and the anode. Such membranes may include polyethylene, polypropylene, polyvinylidene fluoride, or multiple layers thereof, such as polyethylene/polypropylene bi-layer membranes, polyethylene/polypropylene/polyethylene tri-layer membranes, and polypropylene/polyethylene/polypropylene tri-layer membranes.
Lithium secondary batteries may be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the presence of a separator and the type of electrolyte used therein. Rechargeable lithium batteries may have various shapes and sizes, and include cylindrical, square, coin, or pouch type batteries, and may be thin film batteries or may be larger in size. The structure and fabrication methods of lithium ion batteries pertaining to the present disclosure are well known in the art.
Fig. 1 is a schematic view of a representative structure of a lithium secondary battery of the present invention. As shown in fig. 1, the lithium secondary battery 3 is a prismatic battery including: an electrode assembly 4 in a battery case 8, the electrode assembly 4 including a positive electrode 5, a negative electrode 6, and a separator 7 disposed between the positive electrode 5 and the negative electrode 6; an electrolyte solution injected through an upper portion of the case; and a cap plate 11 sealing the battery. The lithium secondary battery of the present invention is not limited to the square shape but may have a cylindrical, coin, or pouch shape as long as the lithium secondary battery including the electrolyte for a lithium secondary battery according to an embodiment of the present invention can operate.
Examples
Hereinafter, examples of the present invention and comparative examples are described. However, these examples are in no way to be construed as limiting the scope of the invention.
Preparation example 1: preparation of electrolyte for lithium secondary battery
An electrolyte was prepared by: ethylene Carbonate (EC), Ethyl Propionate (EP), diethyl carbonate (DEC), and ethyl tert-butyl acetate (compound represented by chemical formula 2-1) were reacted at 3:2:3:2 (ethylene carbonate: ethyl propionate: diethyl carbonate: ethylT-butyl acetate) as a non-aqueous organic solvent, and mixing the mixture with 0.9M LiPF6Mixed, and 6 wt% of fluoroethylene carbonate (FEC), 2.5 wt% of 1, 3-propane sultone (1,3-PS), and 0.5 wt% of ethylene carbonate (VEC) were added thereto as additives, based on the total weight of the electrolyte.
Comparative preparation example 1: preparation of electrolyte for lithium secondary battery
An electrolyte was prepared by: ethylene Carbonate (EC), Ethyl Propionate (EP) and diethyl carbonate (DEC) were mixed in a weight ratio of 3:2:5 (ethylene carbonate: ethyl propionate: diethyl carbonate) as a non-aqueous organic solvent, and the mixture was mixed with 0.9M LiPF6Mixed, and 6 wt% of fluoroethylene carbonate (FEC), 2.5 wt% of 1, 3-propane sultone (1,3-PS), and 0.5 wt% of ethylene carbonate (VEC) were added as additives, based on the total weight of the electrolyte.
Comparative preparation example 2: preparation of electrolyte for lithium secondary battery
An electrolyte was prepared by: ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) were mixed in a weight ratio of 3:2:5 (ethylene carbonate: ethylmethyl carbonate: diethyl carbonate) as a non-aqueous organic solvent, and the mixture was mixed with 0.9M LiPF6Mixed, and 6 wt% of fluoroethylene carbonate (FEC), 2.5 wt% of 1, 3-propane sultone (1,3-PS), and 0.5 wt% of ethylene carbonate (VEC) were added thereto as additives, based on the total weight of the electrolyte.
Comparative preparation example 3: preparation of electrolyte for lithium secondary battery
An electrolyte was prepared by: ethylene Carbonate (EC), Ethyl Propionate (EP) and diethyl carbonate (DEC) were mixed in a weight ratio of 3:4:3 (ethylene carbonate: ethyl propionate: diethyl carbonate) as a non-aqueous organic solvent, and the mixture was mixed with 0.9M LiPF6Mixed, and 6 wt% of fluoroethylene carbonate (FEC), 2.5 wt% of 1, 3-propane sultone (1,3-PS), and 0.5 wt% of ethylene carbonate (VEC) were added thereto as additives, based on the total weight of the electrolyte.
Comparative preparation example 4: preparation of electrolyte for lithium secondary battery
An electrolyte was prepared by: ethylene Carbonate (EC), Ethyl Propionate (EP), diethyl carbonate (DEC) and ethyl butyrate represented by chemical formula 6 were mixed in a weight ratio of 3:2:3:2 (ethylene carbonate: ethyl propionate: diethyl carbonate: ethyl butyrate) as a non-aqueous organic solvent, and the mixture was mixed with 0.9M LiPF6Mixed, and 6 wt% of fluoroethylene carbonate (FEC), 2.5 wt% of 1, 3-propane sultone (1,3-PS), and 0.5 wt% of ethylene carbonate (VEC) were added thereto as additives, based on the total weight of the electrolyte.
[ chemical formula 6]
Figure BDA0001906733310000141
Example 1: production of lithium Secondary Battery cell
Preparing positive electrode active material slurry by: subjecting LiCoO to condensation2A positive electrode active material, a polyvinylidene fluoride binder and Super-P (MMM Co.) No. 94:3:3 (LiCoO)2Polyvinylidene fluoride Super-P) in a weight ratio in an N-methylpyrrolidone solvent as a conductive material. The positive electrode active material slurry was uniformly coated on a 12 μm thick aluminum current collector, dried, and compressed to prepare a positive electrode.
Graphite is used as the negative active material. Graphite (BSG-L)/SBR (BM-440B)/CMC (MAC350, 98/1/1) and a Polyamideimide (PAI) binder were mixed in a weight ratio of 90:10 (graphite: polyamideimide) in an N-methylpyrrolidone solvent to prepare a negative electrode active material slurry. The anode active material slurry was uniformly coated on a 12 μm-thick copper current collector, dried, and compressed to prepare an anode.
553450 prismatic cells were prepared in a conventional manner using the positive and negative electrodes, a polyethylene separator (Ashahi), and the electrolyte prepared according to preparation example 1.
Comparative examples 1 to 4: production of lithium Secondary Battery cell
553450 prismatic cells were each prepared in a conventional manner using the positive and negative electrodes according to example 1, a polyethylene separator (Ashahi), and each of the electrolytes according to comparative preparation examples 1 to 4. The prismatic battery cells were referred to as comparative examples 1 to 4 in this order.
Experimental example 1: cycle life characteristics
The lithium secondary battery cells according to example 1 and comparative examples 1 to 4 were respectively subjected to charge-discharge at a rate of 1C in a range of 3.0V to 4.45V at 45 ℃ for 120 cycles to measure the discharge capacity variation and the retention capacity variation.
Fig. 2 shows the variation of the discharge capacity of the lithium secondary battery cells according to example 1 and comparative examples 1 and 4, and fig. 3 shows the variation of the retention capacity of the lithium secondary battery cells according to example 1 and comparative examples 1 and 4.
As shown in fig. 2, the lithium secondary battery cell according to example 1 maintained the discharge capacity at a comparable level after 100 cycles, the lithium secondary battery cell according to comparative example 1 showed a significant drop in discharge capacity after 70 cycles, and the lithium secondary battery cell according to comparative example 4 showed a significant drop in discharge capacity after 80 cycles.
In addition, as shown in fig. 3, the lithium secondary battery cell according to example 1 maintained the retention capacity at a considerable level after 80 cycles, but the lithium secondary battery cells according to comparative examples 1 and 4 showed a significant drop in retention capacity after 80 cycles.
Therefore, the lithium secondary battery cell according to example 1 exhibited very excellent cycle-life characteristics at high voltage and high temperature, compared to the lithium secondary battery cells according to comparative examples 1 and 4.
Experimental example 2: thickness variation ratio and Internal Resistance (IR) variation ratio
The lithium secondary battery cells according to example 1 and comparative examples 1 to 4 were respectively allowed to stand in order in a thermostat at 45 ℃ for one day, once charged and discharged at 1C rate in the range of 3.0V to 4.45V, allowed to stand for 6 hours, and once charged and discharged at 1C rate in the range of 3.0V to 4.45V. Subsequently, the final rated voltage of each lithium secondary battery cell was checked, and then the lithium secondary battery cells were charged and discharged 100 times at a 1C rate in a thermostat at 45 ℃ in a range of 3.0V to 4.45V, respectively.
Throughout the process, the thickness variation ratio of each lithium secondary battery cell was measured by using a thickness measuring apparatus, a PPG device (TesTop, Mitutoyo Corp.), and the internal resistance variation ratio of each lithium secondary battery cell was measured by using an OCV/IR measuring apparatus (Hioki e.e. Corp.).
Fig. 4 shows the change in thickness of each lithium secondary battery cell according to example 1 and comparative examples 1 and 4, and fig. 5 shows the change in internal resistance of each lithium secondary battery cell according to example 1 and comparative examples 1 and 4.
As shown in fig. 4, the lithium secondary battery cell according to example 1 exhibited a thickness expansion rate of about 22% after 100 cycles, the lithium secondary battery cell according to comparative example 1 exhibited a thickness expansion rate of about 54% after 100 cycles, and the lithium secondary battery cell according to comparative example 4 exhibited a thickness expansion rate of about 34% after 100 cycles.
In addition, as shown in fig. 5, the lithium secondary battery cell according to example 1 showed an internal resistance increase rate of about 53% after 100 cycles, and the lithium secondary battery cell according to comparative example 1 showed an internal resistance increase rate of about 105% after 100 cycles.
Therefore, the lithium secondary battery cell according to example 1 effectively suppresses volume expansion and thus shows significantly superior cycle life characteristics at high voltage and high temperature, compared to the lithium secondary battery cells according to comparative examples 1 and 4.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
< description of the marker >
3: lithium secondary battery, 4: an electrode assembly is provided to be mounted on a main body,
5: positive electrode, 6: a negative electrode, a positive electrode, a negative electrode,
7: diaphragm, 8: a battery case,
11: cover plate

Claims (18)

1. An electrolyte for a lithium secondary battery, comprising:
a non-aqueous organic solvent including a branched ester solvent represented by chemical formula 1; and
lithium salt:
[ chemical formula 1]
Figure FDA0003279800490000011
Wherein, in chemical formula 1,
R1to R4The same or different and independently are C1 to C5 straight or branched chain alkyl groups.
2. The electrolyte for a lithium secondary battery according to claim 1, wherein the branched ester-based solvent represented by chemical formula 1 is selected from the group consisting of: a compound represented by chemical formula 2-1 to a compound represented by chemical formula 2-8 and a combination thereof:
[ chemical formula 2-1]
Figure FDA0003279800490000012
[ chemical formula 2-2]
Figure FDA0003279800490000013
[ chemical formulas 2-3]
Figure FDA0003279800490000014
[ chemical formulas 2-4]
Figure FDA0003279800490000015
[ chemical formulas 2 to 5]
Figure FDA0003279800490000021
[ chemical formulas 2 to 6]
Figure FDA0003279800490000022
[ chemical formulae 2 to 7]
Figure FDA0003279800490000023
[ chemical formulas 2 to 8]
Figure FDA0003279800490000024
3. The electrolyte for a lithium secondary battery according to claim 1, wherein the non-aqueous organic solvent further comprises a solvent selected from the group consisting of: a carbonate-based solvent, a linear ester-based solvent represented by chemical formula 3, and a combination thereof:
[ chemical formula 3]
Figure FDA0003279800490000025
Wherein, in chemical formula 3,
R5and R6The same or different and independently are C1 to C5 straight chain alkyl groups.
4. The electrolyte for a lithium secondary battery according to claim 3, wherein the carbonate-based solvent is selected from the group consisting of: dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and combinations thereof.
5. The electrolyte for a lithium secondary battery according to claim 3, wherein the linear ester solvent represented by chemical formula 3 is selected from the group consisting of: methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, and combinations thereof.
6. The electrolyte for a lithium secondary battery according to claim 3, wherein the non-aqueous organic solvent includes 10 to 40 wt% of the branched ester-based solvent represented by chemical formula 1, based on the total amount of the non-aqueous organic solvent.
7. The electrolyte for a lithium secondary battery according to claim 3, wherein the non-aqueous organic solvent includes the carbonate-based solvent and the linear ester-based solvent represented by chemical formula 3, and the carbonate-based solvent is 100 to 400 parts by weight and the linear ester-based solvent represented by chemical formula 3 is 50 to 150 parts by weight, based on 100 parts by weight of the branched ester-based solvent represented by chemical formula 1.
8. The electrolyte for a lithium secondary battery according to claim 1, wherein the electrolyte for a lithium secondary battery further comprises an electrolyte additive for a lithium secondary battery, and
the electrolyte additive for a lithium secondary battery is selected from the group consisting of: ethylene carbonate-based compounds, alkanesultone, vinylene carbonate, and combinations thereof represented by chemical formula 5:
[ chemical formula 5]
Figure FDA0003279800490000031
Wherein, in chemical formula 5,
R7and R8The same or different and independently selected from the group consisting of: hydrogen, halogen, cyano, nitro, vinyl and fluorinated C1 to C5 straight or branched chain alkyl, provided that R7And R8Not all are hydrogen.
9. The electrolyte for a lithium secondary battery according to claim 8, wherein the alkanesultone is selected from the group consisting of: 1, 3-propane sultone, butane sultone, 1,3- (1-propene sultone), and combinations thereof.
10. The electrolyte for a lithium secondary battery according to claim 8, wherein the electrolyte for a lithium secondary battery comprises 6 to 13 wt% of the electrolyte additive for a lithium secondary battery, based on the total weight of the electrolyte for a lithium secondary battery.
11. The electrolyte for a lithium secondary battery according to claim 8, wherein the electrolyte for a lithium secondary battery comprises fluoroethylene carbonate, 1, 3-propane sultone and ethylene carbonate as the electrolyte additive for a lithium secondary battery.
12. The electrolyte for a lithium secondary battery according to claim 11, wherein the electrolyte additive for a lithium secondary battery comprises 1,000 to 2,000 parts by weight of the fluoroethylene carbonate, 100 to 500 parts by weight of the 1, 3-propane sultone, based on 100 parts by weight of the ethylene carbonate.
13. A lithium secondary battery, comprising:
a positive electrode including a positive active material;
a negative electrode including a negative active material; and
the electrolyte for a lithium secondary battery according to any one of claims 1 to 12.
14. The lithium secondary battery according to claim 13, wherein the positive electrode active material is selected from compounds represented by the following chemical formula:
LiaA1-bDbE2wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0 and less than or equal to 0.5 in the chemical formula; liaG1-bDbO2-cEcWherein in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; LiG2-bDbO4-cEcWherein, in the chemical formula, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; liaNi1-b-cCobDcEαWherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2；LiaNi1-b-cCobDcO2-αJαWherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；LiaNi1-b-cCobDcO2-αJ2Wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；LiaNi1-b-cMnbDcEαWherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2；LiaNi1-b-cMnbDcO2-αJαWherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；LiaNi1-b-cMnbDcO2-αJ2Wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；LiaNibGcLdO2Wherein in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0.001 and less than or equal to 0.2; liaNibGcO2Wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, and c is more than or equal to 0 and less than or equal to 0.5; liaNibCocMndLeO2Wherein in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5,0≤d≤0.5，0.001≤e≤0.2；LiaNibCocMndO2wherein, in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0 and less than or equal to 0.5; liaNiLbO2Wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula; liaCoLbO2Wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula; liaMnLbO2Wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula; liaMn2LbO4Wherein, a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.2 in the chemical formula; liaMn2O4Wherein in the chemical formula, a is more than or equal to 0.90 and less than or equal to 1.8; MO (metal oxide semiconductor)2；MS2；LiMS2；V2O5；LiV2O5；LiQO2；LiNiVO4；Li(3-f)T2(PO4)3Wherein, f is more than or equal to 0 and less than or equal to 2 in the chemical formula; li(3-f)Fe2(PO4)3Wherein, f is more than or equal to 0 and less than or equal to 2 in the chemical formula; LiFePO4，
Wherein formula A is selected from the group consisting of: ni, Co, Mn and combinations thereof, D is selected from the group consisting of: al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and combinations thereof, E is selected from the group consisting of: o, F, S, P and combinations thereof, G is selected from the group consisting of: co, Mn, and combinations thereof, J is selected from the group consisting of: F. s, P, and combinations thereof, L is a transition metal or lanthanide selected from the group consisting of: mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, P, As, Sb, Bi, S, Se, Te, Po, Mn, La, Ce and combinations thereof, M being selected from the group consisting of: ti, Mo, Mn and combinations thereof, Q is selected from the group consisting of: cr, V, Fe, Sc, Ti, Y, and combinations thereof, and T is selected from the group consisting of: v, Cr, Mn, Co, Ni, Cu, and combinations thereof.
15. The lithium secondary battery according to claim 14, wherein the positive electrode active material is LiCoO2。
16. The lithium secondary battery according to claim 13, wherein the negative active material is graphite.
17. The lithium secondary battery according to claim 13, wherein the lithium secondary battery has a charging voltage of 4.3V or more.
18. The lithium secondary battery according to claim 17, wherein the lithium secondary battery has a charging voltage of 4.4V to 4.5V.
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